Chemical compounds

ABSTRACT

Organic compounds having a substituent represented by the formula &lt;IMAGE&gt;   wherein M is alkali metal or ammonium are useful complexing agents for metal and/or alkaline earth metal ions.

This is a continuation, of application Ser. No. 471,088, filed May 17,1974, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novel compounds useful as complexing agentsfor various metal and/or alkaline earth metal ions and to detergentformulations containing such compounds as functional ingredients.

It is well recognized that compounds having the ability to complex metaland/or alkaline earth metal ions which contribute to water "hardness",e.g. magnesium and calcium are useful in a variety of applications suchas water treatment (e.g., softening, scale inhibition). (It is notedthat some complexing agents also exhibit the ability of preventingprecipitation of hardness ions from water even when used in quantitiesstoichiometrically insufficient to sequester the hardness ions. Suchagents are said to exhibit "threshold" effect). Additionally, some suchcompounds exhibit the ability to enhance, potentiate or supplement thecleaning ability of detergent formulations and are useful as functionalingredients thereof. Conventionally, such ingredients are referred to asdetergency "builders" although in some applications, e.g., machinedishwashing formulations, the functionality of such compounds appears tobe more than or different from a mere "building" of the performance ofother ingredients of the formulation.

The provision of novel complexing agents has long been a continuingobjective of those skilled in the art in view of the varied, recognizedutilities of such materials.

SUMMARY OF THE INVENTION

It is an object of this invention to provide novel compounds useful ascomplexing agents for various metal and/or alkaline earth metal ions --particularly ions such as magnesium and calcium -- and which are usefulas functional ingredients in detergent formulations and/or exhibitsurface active properties.

The compounds of the invention are characterized by the presence of atleast one ##STR2## substituent (M, being alkali metal or ammonium).These compounds, their preparation and use will be understood from thefollowing description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds of the present invention correspond to alcohols having anactive alcoholic hydroxy group replaced with a substituent representedby the formula ##STR3## wherein M is alkali metal or ammonium and acidsand esters thereof, provided, that the moiety to which the ##STR4##substituent is attached is other than ##STR5## wherein A and A' arehydrogen or methyl.

The term "active alcoholic hydroxy group" is used to denote an alcoholichydroxy group convertable to a conjugate base group reactive withdiethyl ketomalonate to form a substituent represented by the formula##STR6## (The --O⁻ will, of course be associated with the cation of theconjugate base, e.g. --O⁻ Na⁺)

The conversion of alcohols to their conjugate base forms is wellunderstood. The conjugate base is obtained by reacting the alcohol witha base sufficiently strong to deprotonate a hydroxy group. Generally,deprotonization of reactive hydroxy groups is readily accomplished withsodium, potassium, sodium hydride, potassium hydride, sodium orpotassium t-butoxide, sodium or potassium amide, etc. The reaction isconveniently conducted at temperatures of the order of 0° C. to 115° C.in any solvent for the alcohol which is not adversely reactive with thestrong base. Examples of solvents suitable for use with various alcoholsinclude, tetrahydrofuran, dimethylsulfoxide, dimethylformamide,ethylether, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, or the like.In those instances where the reactant alcohol is a liquid, an excess ofsuch alcohol may be employed as the solvent. Mixed solvents can be used,if desired. More detailed discussion of the conversion of alcohols toconjugate bases is found in such references as Morrison and Boyd,Organic Chemistry, 3rd edition, Allyn and Bacon, Inc. (1973) pp. 526,527; Feuer and Hooz, The Chemistry of the Ether Linkage, edited byPatai, Interscience Publishers (1967), Chapter 10, p. 447; and Schmidtand Bayer, Methoden Der Organischen Chemie (Houben-Weyl) Band VI/2,Georg Theime Verlag, (1963) Saurstoff Vergindunger 1, Teil 2 andbibliographies provided in the foregoing references.

The conjugate base form of the alcohol is then reacted with anhydrousdiethylketomalonate, preferably at temperatures of from -50° to 60° C.and preferably in the solvent used for preparation of the conjugatebase. The occurrence of the reaction is readily detected by conventionalanalytical techniques e.g. hydrogen or carbon 13 nuclear magneticresonance spectral shifts or by observance of the disappearance of thecharacteristic yellow to yellow-green color of anhydrousdiethylketomalonate.

When polydroxy alcohols are reacted as above resulting ##STR7##substituents may undergo transesterification with other stericallyaccessible hydroxy groups of the alcohol to form a cyclic lactonecontaining a moiety. ##STR8## Thus, when an alcohol is tested inreactions as described above to determine if all or some of its hydroxygroups are "active" the formation of either a ##STR9## substituent or alactone containing a ##STR10## moiety confirms the presence of an activehydroxy group.

By way of further description, the compounds of this invention can berepresented by the formula ##STR11## in which R is an organic radicalcorresponding to the residue of an alcohol having at least one activealcoholic hydroxy group removed therefrom and a is an integer equal tothe number of hydroxy groups removed from the corresponding alcohol.

Although the compounds of this invention are described above byreference to analogous alcohols and are, as hereinafter explained,preferably derived from alcohols, no intention to limit the compounds ofthis invention to those actually derived from alcohols should beimplied. In fact, the compounds of this invention can be prepared bysynthetic techniques not requiring active hydroxy containing compoundsas precursors. Therefore, this mode of description is merely intended tofacilitate an understanding of the scope of the invention.

Examples of the compounds of this invention include ##STR12##substituted:

(a) alkanes such as ##STR13## (The above two compounds are particularlypreferred embodiments of the invention in view of excellent performanceas detergency builders. It is further noted that these compounds arereadily biodegradable which is quite unexpected in view of theresistance to biodegradability of a carboxylated analog, ##STR14## whichanalog is disclosed in U.S. Pat. No. 3,742,045.) ##STR15## (Substitutedlong chain alkanes, e.g. C₁₀ to C₂₀, of this type exhibit surface activeproperties as well as complexing properties and are, therefore,additionally useful as emulsifiers, foaming agents, etc.); ##STR16##

(b) cycloalkanes such as ##STR17##

(d) ethers such as ##STR18##

(e) aromatics such as ##STR19##

The moieties to which the ##STR20## substituents are attached may bearother substituents which are not chemically incompatible with themoiety. ##STR21##

For convenience, the compounds of this invention have been exemplifiedabove in the salt forms; however, the corresponding ester and acid formswill be apparent to those skilled in the art. It is pointed out that insome instances, for example in the case of a compound such as ##STR22##the corresponding ester and acid forms may exhibit a lactone structuresuch as ##STR23##

The compounds of this invention are most conveniently prepared byreacting an alcohol containing an active alcoholic hydroxy group with astrong base to form the conjugate base form for the alcohol. Suchreactions have previously been described in the discussion of thedefinition of "active alcoholic hydroxy groups". In general, the use ofsodium or potassium metals or hydrides to convert -- OH groups to --O⁻Na⁺ or --O⁻ K⁺ groups is preferred in the case of alcohols sufficientlyacidic to react with these bases.

The conjugate base form of the alcohol is then reacted with aketamalonate ester ##STR24## which will convert the --O⁻ substituent toa ##STR25## substituent, or may, if for example the --O⁻ substituent isattached to a carbon atom adjacent to an hydroxy substituted carbon atomform a lactone containing the moiety. ##STR26## In the above formulae, Xmay be any organic moiety which will not, by virtue of chemicalreactivity or stearic hindrance, interfere with the reaction. Thereaction will proceed in all cases wherein X is a lower alkyl such asmethyl or ethyl. However, it is generally desirable, where permissiblefrom the standpoint of chemical reactivity and stearic hindrance, that Xcorrespond to the organic moiety to which the conjugate base form of thealcoholic hydroxy group is attached in order to prevent formation of amixture of products via transesterification reactions and thedifficulties attendant to separation of such mixtures.

The reaction with the ketomalonate ester is preferably conducted in thesame solvent system used in converting the alcohol to its conjugate baseat temperatures from -50° to 60° C., preferably from -20° to 30° C.Alternatively, the alcohol can first be reacted with the ketomalonateester followed by reaction with strong base to form the ##STR27##containing product. Generally, however, conversion of the alcohol to itsconjugate base form followed by reaction with the ester is preferred.

When the starting alcohol contains more than one active hydroxy group,the quantities of reactants and severity of reaction conditions employedin the foregoing reaction will determine whether only one or more ofsuch groups are replaced in the reactions.

The ##STR28## containing product is then reacted with bromo or iodoacetate ZCH₂ COOX (Z is Br or I) to convert the --O⁻ substituent to a--OCH₂ COOX substituent thereby yielding the ester form of the compoundsof the invention.

The bromoacetate or iodoacetate may be added as such or produced insitu, e.g., by using a mixture of sodium iodide and chloroacetate.Reaction temperatures are not critical, a temperature range of -20° to100° C. usually being satisfactory.

In general, the reactions described can be conducted at atmosphericpressure, although, in some instances, it may be desirable to providereflux means or pressure to prevent excessive loss of reactants orsolvents, or to permit use of higher temperatures.

Reaction of the esters with alkali metal hydroxide yields the alkalimetal salt forms of the compounds of the invention which can beconverted to the acid form by acidulation (for example, by means of astrong acid ion exchange resin such as sulfonated polystyrene or astrong mineral acid.

Reaction of the acid form with ammonium hydroxide will yield theammonium salt forms of the compounds of this invention.

As discussed above, the acid and ester forms of the compounds of thisinvention are useful as intermediates for preparation of the salt forms.

The ##STR29## substituents of the compounds of this invention providesequestrant and detergency builder functionality. Other usefulfunctionality may be provided by the moiety to which the ##STR30##substituents are attached.

As seen from the foregoing discussion, the moieties to which ##STR31##substituents may be attached include aliphatic, alicyclic, aromatic,alkyl aromatic, alcohol, and ether moieties.

Preferred classes of the compounds of this invention are those in whichthe moiety to which the ##STR32## substituents are attached are: (1) analkane containing 1 to 20 carbon atoms. Substituted C₁ to C₄ alkanesprovide particularly effective builder functionality whereas the higheralkanes additionally provide surfactant functionality.

(2) polyalkylene oxides particularly polyethylene oxides containing 2 to20 molecular proportions of ethylene oxide are effective solubilizingagents having sequestrant properties.

(3) alkyl benzenes (preferably having alkyl chains containing 5 to 20,most preferably 8 to 15 carbon atoms) are surfactants havingsequestering properties. Compounds wherein the ##STR33## substituent isattached to the benzene ring are particularly preferred.

In general, compounds in which the ##STR34## substituents constitute atleast 50%, preferably at least 85% of the weight of the compound arepreferred for applications wherein sequestrant or builder functionalityis of primary importance. It is further generally preferred that suchsubstituents be attached to uncarboxylated carbon atoms. Generally,compounds having one or two of such substituents are preferred from thestandpoint of ease of synthesis.

In detergency builder applications, the use of the alkali metal salts,particularly the sodium salt is preferred. However, in some formulations(such as liquid formulations where greater builder solubility isrequired) the use of ammonium or alkanol ammonium salts may bedesirable.

The detergent formulations will contain at least 1% by weight andpreferably at least 5% by weight of the salt forms of compounds of thisinvention. In order to obtain the maximum advantages of the buildercompositions of this invention, the use of from 5% to 75% of these saltsis particularly preferred. The salt compounds of this invention can bethe sole detergency builder or these compounds can be utilized incombination with other detergency builders which may constitute from 0to 95% by weight of the total builders in the formulation. By way ofexample, builders which can be employed in combination with the novelsalt compounds of this invention include water soluble inorganic buildersalts such as alkali metal polyphosphates, i.e., the tripolyphosphatesand pyrophosphates, alkali metal carbonates, borates, bicarbonates andsilicates and water soluble organic builders including aminopolycarboxylic acids and salts such as alkali metal nitrilotriacetates,cycloalkane polycarboxylic acids and salts, ether polycarboxylates,alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuranpolycarboxylates such as 1,2,3,4 or 2,2,5,5 tetrahydrofurantetracarboxylates, benzene polycarboxylates, oxidized starches, amino(trimethylene phosphonic acid) and its salts, diphosphonic acids andsalts (e.g. methylene diphosphonic acid; 1-hydroxy ethylidenediphosphonic acid) and the like.

The detergent formulations will generally contain from 5% to 95% byweight total builder (although greater or lesser quantities may beemployed if desired) which, as indicated above, may be solely thebuilder salt compounds of this invention or mixtures of such compoundswith other builders. The total amount of builder employed will bedependent on the intended use of the detergent formulation, otheringredients of the formulation, pH conditions and the like. For example,general laundry powder formulations will usually contain 20% to 60%builder; liquid dishwashing formulations 11% to 12% builder; machinedishwashing formulations 60% to 90% builder. Optimum levels of buildercontent as well as optimum mixtures of builders of this invention withother builders for various uses can be determined by routine tests inaccordance with conventional detergent formulation practice.

The detergent formulations will generally contain a water solubledetergent surfactant although the surfactant ingredient may be omittedfrom machine dishwashing formulations. Any water soluble anionic,nonionic, zwitterionic or amphoteric surfactant can be employed.

Examples of suitable anionic surfactants include soaps such as the saltsof fatty acids containing about 9 to 20 carbon atoms, e.g. salts offatty acids derived from coconut oil and tallow; alkyl benzenesulfonates--particularly linear alkyl benzene sulfonates in which thealkyl group contains from 10 to 16 carbon atoms; alcohol sulfates;ethoxylated alcohol sulfates; hydroxy alkyl sulfonates; alkenyl andalkyl sulfates and sulfonates; monoglyceride sulfates; acid condensatesof fatty acid chlorides with hydroxy alkyl sulfonates and the like.

Examples of suitable nonionic surfactants include alkylene oxide (e.g.,ethylene oxide) condensates of mono and polyhydroxy alcohols, alkylphenols, fatty acid amides, and fatty amines; amine oxides; sugarderivatives such as sucrose monopalmitate; long chain tertiary phosphineoxides; dialkyl sulfoxides; fatty acid amides, (e.g., mono or diethanolamides of fatty acids containing 10 to 18 carbon atoms), and the like.

Examples of suitable zwitterionic surfactants include derivatives ofaliphatic quaternary ammonium compounds such as3-(N,N-dimethyl-N-hexadecyl ammonio) propane-1-sulfonate and3-(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxy propane-1-sulfonate.

Examples of suitable amphoteric surfactants include betains,sulfobetains and fatty acid imidazole carboxylates and sulfonates.

It will be understood that the above examples of surfactants are by nomeans comprehensive and that numerous other surfactants are known tothose skilled in the art. It will be further understood that the choiceand use of surfactants will be in accordance with well understoodpractices of detergent formulation. For example, anionic surfactants,particularly linear alkyl benzene sulfonate are preferred for use ingeneral laundry formulations, whereas low foaming nonionic surfactantsare preferred for use in machine dishwashing formulations.

The quantity of surfactant employed in the detergent formulations willdepend on the surfactant chosen and the end use of the formulation. Ingeneral, the formulations will contain from 5% to 50% surfactant byweight, although as much as 95% or more surfactant may be employed ifdesired. For example, general laundry powder formulations normallycontain 5% to 50%, preferably 15% to 25% surfactant; machine dishwashingformulations 0.5% to 5%; liquid dishwashing formulations 20% to 45%. Theweight ratio of surfactant to builder will generally be in the range offrom 1:12 to 2:1.

In addition to builder and surfactant components, detergent formulationsmay contain fillers such as sodium sulfate and minor amounts ofbleaches, dyes, optical brightners, soil anti-redeposition agents,perfumes and the like.

In machine dishwashing compositions the surfactant will be a low-foaminganionic or preferably, nonionic surfactant which will constitute 0 to 5%of the formulation.

The term "low-foaming" surfactant connotes a surfactant which, in thefoaming test described below, reduces the revolutions of the washerjet-spray arm during the wash and rinse cycles less than 15%, preferablyless than 10%.

In the foaming test, 1.5 grams of surfactant is added to a 1969Kitchen-Aid Home Dishwasher, Model No. KOS-16, manufactured by HobartManufacturing Company which is provided with means for countingrevolutions of the washer jet-spray arm during wash and rinse cycles.The machine is operated using distilled water feed at a machine entrancetemperature of 40° C. The number of revolutions of the jet-spray armduring the wash and rinse cycles is counted. The results are comparedwith those obtained by operation of the machine using no surfactantcharge and the percentage decrease in the number of revolutions isdetermined.

The surfactant should, of course, be compatible with the chlorinecontaining component hereinafter discussed. Examples of suitablenonionic surfactants include ethoxylated alkyl phenols, ethoxylatedalcohols (both mono- and di- hydroxy alcohols), polyoxyalkylene glycols,aliphatic polyethers and the like. The widely commercially utilizedcondensates of polyoxypropylene glycols having molecular weights of fromabout 1400 to 2200 with ethylene oxide (the ethylene oxide constituting5 to 35 weight percent of the condensate) are, for example,advantageously used in the machine dishwashing formulations of thisinvention.

Suitable low-foaming anionic surfactants include alkyl diphenyl ethersulfonates such as sodium dodecyl diphenyl ether disulfonates and alkylnaphthalene sulfonates.

Mixtures of suitable low-foaming surfactants can be utilized if desired.

In addition, machine dishwashing formulations will contain sufficientchlorine providing compound to provide 0.5% to 2% available chlorine.For example, the formulation may contain from 0.5% to 5%, preferably 1%to 3% of a chlorocyanurate or from 10% to 30% chlorinated trisodiumphosphate. Suitable chlorocyanurates are sodium and potassiumdichlorocyanurate; [(monotrichloro) tetra-(monopotassium dichloro)]penta-isocyanurate; (monotrichloro) (monopotassium dichloro)diisocyanurate.

Machine dishwashing compositions should additionally contain from 5% to30% soluble sodium silicate having an SiO₂ to Na₂ O mole ratio of from1:1 to 3.2:1 preferably about 2.4:1 to inhibit corrosion of metal partsof dishwashing machines and provide over-glaze protection to fine china.

Machine dishwashing compositions will generally contain at least 10%,preferably at least 20% builder, up to a maximum of about 90% builder.The new salt compounds of this invention should constitute at least 5%of the weight of the machine dishwashing formulation.

The invention is further illustrated by the following examples whereinall parts and percentages are by weight unless otherwise indicated.

EXAMPLE I

A slurry of 70 grams sodium hydride in 1500 ml. tetrahydrofuran isprepared and 125 ml. methanol is added, the temperature being maintainedbelow 35° C. The mixture is stirred for about 1 hour at 25° to 30° C.and cooled to about 0° C. About 409 grams dimethyl ketomalonate isadded, following which 444 grams methyl bromoacetate is added. Themixture is stirred for about 1 hour, the temperature being maintainedbelow 10° C. The temperature is then slowly raised and the reactionmixture refluxed for 18 hours.

The tetrahydrofuran is evaporated and the residue dissolved in a mixtureof water and ethyl ether. The mixture is allowed to separate and theproduct containing ether layer is removed and washed with water. Theether is dried over CaSO₄, evaporated and the residue vacuum distilledwith trimethyl 2-(carboxymethoxy)-2-methoxymalonate ##STR35## productbeing collected at 110° to 113° C./0.05 mm Hg. A solution of 466 gramsof the above ester product in 466 grams methanol is added to 1000 gramsof 25% sodium hydroxide aqueous solution. (After about 1/2 of the estersolution has been added, the temperature is about 60° C. and 200 ml.water is added; ester addition is completed and 300 ml. water and 500ml. methanol are added.)

The slurry is cooled to about 25° C. with stirring and filtered. Thesolid product is trisodium 2-(carboxymethoxy)-2-methoxymalonate.##STR36##

EXAMPLE II

A slurry of 41.6 grams sodium hydride in 1200 ml. tetrahydrofuran isprepared and 130 ml. ethanol added, the temperature being maintainedbelow 30° C. The mixture is cooled to about 5° C. and maintained at thattemperature for about 2 hours after which 400 grams diethyl ketomalonateis added, the temperature being maintained below 10° C. Ethylbromoacetate (384 grams) is then added and the temperature maintainedbelow 5° C. for 2 hours. The mixture is then warmed to 25° C. andmaintained at about that temperature for 12 hours with stirring. Thetemperature is then raised to and maintained at 40° C. for 1 hour.

The tetrahydrofuran is evaporated and the residue dissolved in ether andwashed with water. The ether fraction is separated and dried overcalcium sulfate. The ether is evaporated and the product triethyl2-(carboxymethoxy)-2-ethoxymalonate ##STR37## separated from the residueby distillation.

A solution of 547 grams of the above ester product in 200 ml. ethanol isadded to 1020 grams 25% sodium hydroxide aqueous solution, thetemperature being maintained below 45° C. The mixture becomes thick and300 ml. ethanol is added to provide a stirrable slurry which is warmedto 45° C., cooled to 25° C. after 2 hours, and allowed to stand for 12hours. Additional ethanol (100 ml.) is added and the slurry filtered toseparate the solid trisodium 2-(carboxymethoxy)-2-ethoxymalonateproduct. ##STR38##

EXAMPLE III

A solution of 58 grams dodecyl alcohol in 50 ml. dimethyl formamide isadded, at 25° C., to a slurry of 7 grams sodium hydride in 500 ml.dimethyl formamide. The mixture is stirred at 25° C. for 1 hour and thenat 40° C. for an additional hour.

The mixture is cooled to about -20° C. and 50 grams of diethylketomalonate is added. After several minutes stirring, 48 grams of ethylbromoacetate is added, the temperature being maintained between -7° and-30° C. The reaction mixture is allowed to warm to 25° C. and is stirredfor 12 hours.

The product ester triethyl 2-(carboxymethoxy)-2-dodecoxymalonate##STR39## is separated by extraction with ethyl ether and purified bydistillation.

About 75 grams of the above ester product in 50 ml. methanol is added to125 grams of 25% sodium hydroxide aqueous solution cooled with an icebath. An additional 100 ml. methanol is added and the resultant slurryis stirred for 1 hour at 25° C. The slurry is then filtered to separatesolid trisodium 2-(carboxymethoxy)-b 2-dodecoxymalonate product.##STR40##

EXAMPLE IV

Diethylene glycol (14 grams) is added to a slurry of about 6.4 gramssodium hydride in 300 ml. dimethyl formamide. The mixture is cooled to0° C. and, stirred until reaction appears complete, and cooled to -50°C. About 50 grams diethyl ketomalonate is added followed by addition of48 grams ethyl bromoacetate. The temperature is raised slowly to about-20° C. at which point foaming is observed. After foaming ceases, thetemperature is raised to 25° C. the mixture is stirred for 12 hours.

The dimethyl formamide is evaporated and the product residue hexaethyl4,4,12,12-tetracarboxy-3,5,8,11,13-pentaoxapentadecandioate ##STR41##purified by washing with water and molecular distillation.

Reaction of the above ester with aqueous sodium hydroxide yieldshexasodium 4,4,12,12-tetracarboxy-3,5,8,11,13-pentaoxapentadecandioate##STR42##

EXAMPLE V

A solution of 10 grams phenol in dimethyl formamide is added to a slurryof 24 grams sodium hydride in 500 ml. dimethyl formamide. Uponcompletion of reaction, the mixture is cooled to -20° C. and 174 gramsdiethyl ketomalonate is added followed by 167 grams ethyl bromoacetate.

The mixture is warmed to room temperature and stirred for two hours.

The ester product triethyl 2-(carboxymethoxy)-2-phenoxymalonate##STR43## is converted to the salt trisodium2-(carboxymethoxy)-2-phenoxymalonate ##STR44## by reaction with aqueoussodium hydroxide.

EXAMPLE VI-XLIX

One mole of the active hydroxy containing compounds shown in Table I,below is slowly added to a slurry of 24 grams sodium hydride in dimethylformamide or tetrahydrofuran solvent. The quantity of solvent issufficient to render the reaction mixture stirrable and additionalsolvent is added during the reaction as required. One mole of diethylketomalonate is added while maintaining the temperature as low asconsistent with reasonable reaction rate in order to minimize formationof by-products via transesterification.

One mole of ethyl bromoacetate is added and the temperature increased toabout 70° C.

Upon completion of the reaction, the solvent is removed under reducedpressure and the product ester residue shown in Table I, below, ispurified by conventional extraction and/or distillation techniques.

The ester is dissolved in ethanol and reacted wih aqueous sodiumhydroxide to yield the salt product shown in Table I.

    TABLE I       Hydroxy Containing   Example Compound Ester Product (5) Salt Product     (5)           VI C.sub.20 H.sub.41      OH     ##STR45##      ##STR46##      VII     ##STR47##      ##STR48##      ##STR49##      VIII     ##STR50##      ##STR51##      ##STR52##      IX     ##STR53##      ##STR54##      ##STR55##      X     ##STR56##      ##STR57##      ##STR58##      XI     ##STR59##      ##STR60##      ##STR61##      XII     ##STR62##      ##STR63##      ##STR64##      XIII     ##STR65##      ##STR66##      ##STR67##      XIV     ##STR68##      ##STR69##      ##STR70##      XV     ##STR71##      ##STR72##      ##STR73##      XVI     ##STR74##      ##STR75##      ##STR76##       XVII     ##STR77##      ##STR78##      ##STR79##      XVIII     ##STR80##      ##STR81##      ##STR82##      XIX     ##STR83##      ##STR84##      ##STR85##      XX     ##STR86##      ##STR87##      ##STR88##      XXI     ##STR89##      ##STR90##      ##STR91##      XXII     ##STR92##      ##STR93##      ##STR94##       XXIII     ##STR95##      ##STR96##      ##STR97##      XXIV     ##STR98##      ##STR99##      ##STR100##      XXV     ##STR101##      ##STR102##      ##STR103##      XXVI     ##STR104##      ##STR105##      ##STR106##      XXVII     ##STR107##      ##STR108##      ##STR109##      XXVIII     ##STR110##      ##STR111##      ##STR112##      XXIX     ##STR113##      ##STR114##      ##STR115##      XXX     ##STR116##      ##STR117##      ##STR118##      XXXI     ##STR119##      ##STR120##      ##STR121##       XXXII CH.sub.3 OCH.sub.2 CH.sub.2      OH     ##STR122##      ##STR123##      XXXIII     ##STR124##      ##STR125##      ##STR126##      XXXIV     ##STR127##      ##STR128##      ##STR129##      XXXV     ##STR130##      ##STR131##      ##STR132##       XXXVI HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH      ##STR133##      ##STR134##         and and      ##STR135##      ##STR136##      XXXVII     ##STR137##      ##STR138##      ##STR139##      XXXVIII     ##STR140##      ##STR141##      ##STR142##       XXXIX CH.sub.3 (CH.sub.2).sub.7 CHCH(CH.sub.2).sub.7 CH.sub.2 OH      ##STR143##      ##STR144##       XL H(CH.sub.2).sub.5 CHCHCH.sub.2 CHCH(CH.sub.2).sub.8      OH     ##STR145##      ##STR146##       XLI H(CH.sub.2).sub.8 CC(CH.sub.2).sub.8      OH     ##STR147##      ##STR148##      XLII     ##STR149##      ##STR150##      ##STR151##      XLIII     ##STR152##      ##STR153##      ##STR154##      XLIV     ##STR155##      ##STR156##      ##STR157##       XLV HO(CH.sub.2).sub.5      OH     ##STR158##      ##STR159##         and and      ##STR160##      ##STR161##      XLVI HO(CH.sub.2).sub.20      OH     ##STR162##      ##STR163##        and and     ##STR164##      ##STR165##      XLVII     ##STR166##      ##STR167##      ##STR168##        and and     ##STR169##      ##STR170##      XLVIII     ##STR171##      ##STR172##      ##STR173##        and and      ##STR174##      ##STR175##      XLVIX     ##STR176##      ##STR177##      ##STR178##      ##STR179##      ##STR180##

EXAMPLE L

The product salts prepared according to Examples I through XLIX whentested for sequestration function using the procedures described byMatzner et al., "Organic Builder Salts as Replacements for SodiumTripolyphosphate", Tenside Detergents, 10, Heft 3, pages 119-125 (1973),are found to be effective sequestrants.

EXAMPLE LI

Detergent formulations containing 50% of the builder shown in Table 2below; 17% linear alkylbenzene sulfonate having an average molecularweight of about 230; 6% sodium silicate; remainder, sodium sulfate areprepared. The formulations are tested by washing identically soiledfabric swatches (indicated in the Table) in water of 200 ppm hardness at49° C. containing 0.15% detergent formulation using identical washingtechniques. The reflectivity of the soiled swatches before and afterwashing is measured instrumentally and the difference reported in Table2 as Δ Rd. High Δ Rd values are indicative of correspondingly highdetergency effectiveness.

                  Table 2                                                         ______________________________________                                                                       Polyester/                                                            Cotton  Cotton                                                                Fabric  Fabric                                         Builder                Δ Rd                                                                            Δ Rd                                     ______________________________________                                        none (a filler-                                                               sodium sulfate-                                                               is used in place                                                              of builder)            <13     <5                                              ##STR181##            16.9    8.3                                             ##STR182##            14.6    8.0                                             ##STR183##            14.4    6.4                                             ##STR184##            15.2    8.9                                            ______________________________________                                    

the data presented in Table 2 show the salt forms of the compounds ofthis invention to be effective detergency builders.

EXAMPLE LII

Aqueous solutions of the salt products prepared according to Examples Ithrough XLIX are reacted with hydrochloric acid to yield thecorresponding acid forms. Reaction of the acids with ammonium hydroxideyields the corresponding ammonium salts which are found to be effectivesequestrants when tested according to the procedure referred in ExampleL.

What is claimed is:
 1. A compound corresponding to the following formula##STR185## wherein M is alkali metal or ammonium and acids and estersthereof, and wherein n is a number from 1 through 3, and wherein R isselected from an alkyl radical having from 1 to 20 carbon atoms, analkenyl radical having from 1 to 20 carbon atoms, an alkynyl radicalhaving from 1 to 20 carbon atoms, an alkanol radical having from 2 to 20carbon atoms, and an ether radical having at least 3 carbon atoms.
 2. Acompound according to claim 1 wherein the radical within the parenthesesis attached to an uncarboxylated carbon atom.
 3. A compound according toclaim 1 wherein the radical within the parentheses constitute at least50% of the total weight of the compound.
 4. A compound according toclaim 1 wherein the radical within the parentheses constitute at least85% of the total weight of the compound.
 5. A compound according toclaim 1 wherein the moiety to which the radical within the parenthesesis attached is an alcohol moiety.
 6. A compound according to claim 1wherein the moiety to which the radical within the parentheses isattached is an ether moiety.
 7. A compound according to claim 1 whereinthe moiety to which the radical within the parentheses is attached is apoly (alkylene oxide) moiety.
 8. A compound according to claim 1 whereinthe moiety to which the radical within the parentheses is attached is amoiety represented by the formula

    C.sub.n H.sub.2n+1

wherein n is an integer from 1 to
 20. 9. A compound according to claim 1wherein the moiety to which the radical within the parentheses isattached is CH₃
 10. A compound according to claim 1 wherein the moietyto which the radical within the parentheses is attached is

    CH.sub.3 CH.sub.2